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Electronic states, conical intersections, and spin-rovibronic spectroscopy of the nitrogen oxide sulfide radical
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10.1063/1.4794313
/content/aip/journal/jcp/138/10/10.1063/1.4794313
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/10/10.1063/1.4794313

Figures

Image of FIG. 1.
FIG. 1.

MRCI one-dimensional cuts of 3D-PESs of SNO electronic states along the bending angle (θ), where the distances are set to RSN = 1.58 Å and RON = 1.19 Å. The zero energy corresponds to the energy of the S(3P)+ NO(X2Π) asymptote.

Image of FIG. 2.
FIG. 2.

Collinear MRCI potential energy curves of the lowest electronic states of SNO along the ON distance (RON) where the SN distance (RSN) is kept fixed to RSN = 1.58 Å. These curves are positioned in energy with respect to the energy of the S(3P)+NO(X2Π) asymptote.

Image of FIG. 3.
FIG. 3.

Collinear MRCI potential energy curves of the lowest electronic states of SNO along the SN distance (RSN) where the ON distance (RON) is kept fixed to RON = 1.19 Å. These curves are positioned in energy with respect to the energy of the S(3P)+NO(X2Π) asymptote.

Image of FIG. 4.
FIG. 4.

MRCI one-dimensional cuts of the 3D-PESs of the lowest doublet and quartet electronic states of SNO by stretching the ON distance (RON) for bent structures. The SN distance is kept fixed to RSN = 1.58 Å. The zero energy corresponds to the energy of the S(3P)+NO(X2P) asymptote.

Image of FIG. 5.
FIG. 5.

MRCI one-dimensional cuts of the 3D-PESs of the lowest doublet and quartet electronic states of SNO along the SN distance (RSN) for bent structures. The ON distance is kept fixed to RON = 1.19 Å. The zero energy corresponds to the energy of the S(3P)+NO(X2Π) asymptote.

Image of FIG. 6.
FIG. 6.

HOMO and LUMO of SNO obtained at the CASSCF/aug-cc-pVQZ level for bent (upper trace) and linear (lower trace) configurations.

Image of FIG. 7.
FIG. 7.

Schematic representation of the complex dynamics on the lowest doublet electronic states of SNO (i) excitation, (ii) evolution of the wavepacket on the 22A potential, (iii) conversion to the 12A, (iv) conversion to the 2A at linearity by Renner–Teller coupling, (v) conversion to the 2A after vibronic coupling at the 22A- 2A avoided crossing, (vi) dissociation to form S(3P)+NO(X2Π). The zero energy corresponds to the energy of the S(3P)+NO(X2Π) asymptote.

Image of FIG. 8.
FIG. 8.

Pattern of the a spin-rovibronic levels of SNO 2A (upper trace) and of 2A(Π) (lower trace) vs Ka quantum number as listed in Tables S4 and S5 of Ref. 49 .

Image of FIG. 9.
FIG. 9.

Contour plots of the SNO( 2A) vibrational wavefunctions of the (0,0,2), the (1,0,0), and the (0,7,0) levels along the ON stretching and the bending coordinates (left) and along the SN stretching and the bending coordinates (right). The remaining distances were fixed at their equilibrium values for SNO( 2A).

Image of FIG. 10.
FIG. 10.

Tables

Generic image for table
Table I.

MRCI/aug-cc-pV5Z vertical excitation energies (Tv in eV) and dominant electron configuration of the electronic states of SNO for bent configurations. They are quoted at the equilibrium geometry of the ground state, i.e., RON = 1.19 Å, RSN = 1.58 Å, and θ = 139.97°.

Generic image for table
Table II.

MRCI/aug-cc-pV5Z vertical excitation energies (Tv in eV) and dominant electron configuration of the electronic states of SNO for linear configurations. They are quoted at the minimum of the lowest 2Π (Figures 2 and 3 ).

Generic image for table
Table III.

Optimized equilibrium geometries, harmonic vibrational frequencies (in cm−1), and rotational constants at equilibrium (Ae, Be, Ce, in GHz) for the 2A ground state of SNO. Distances are in Å and angles are in degrees.

Generic image for table
Table IV.

Optimized equilibrium geometries, harmonic vibrational frequencies (in cm−1), and rotational constant at equilibrium (Be, in GHz) for the 2A(Π) state of SNO. Distances are in Å and angles are in degrees.

Generic image for table
Table V.

τ constants, first-order centrifugal distortion constants, harmonic, and anharmonic vibrational constants for SNO. These data are derived using our RCCSD(T)/cc-pVTZ-F12 3D-PESs and second order perturbation theory. Dimensional constants are in cm−1.

Generic image for table
Table VI.

Variationally computed rovibronic levels of 32S14N16O( 2A) up to ∼3000 cm−1 for J = ½ and their tentative assignment. We used our RCCSD(T)-F12/cc-pVTZ-F12 3D-PESs. See Ref. 49 for further details.

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/content/aip/journal/jcp/138/10/10.1063/1.4794313
2013-03-14
2014-04-25
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Electronic states, conical intersections, and spin-rovibronic spectroscopy of the nitrogen oxide sulfide radical
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/10/10.1063/1.4794313
10.1063/1.4794313
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